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Unleashing phosphorus mononitride

Edin, Simon LU ; Sandoval-Pauker, Christian ; Yutronkie, Nathan J. ; Takacs, Zoltan LU ; Wilhelm, Fabrice ; Rogalev, Andrei ; Pinter, Balazs ; Pedersen, Kasper S. and Reinholdt, Anders LU (2025) In Nature Communications 16(1).
Abstract

The interstellar diatomic molecule, phosphorus mononitride (P≡N), is highly unstable under conditions typical on Earth, and its utility for constructing elusive P–N π-bonded motifs has remained uncertain. Here, we show how Na(OCP) transfers a P atom to an electrophilic osmium nitride complex to form a metal-bound P≡N ligand. Quantum chemical calculations and X-ray absorption spectroscopy unveil a cumulenic [OsIV=N=P] electronic structure comprising orthogonal Os=N and N=P π-bonding. On reaction with elemental sulfur, the highly reduced P≡N ligand, formally [PN]2–, forms a trigonal planar [NPS2]2– motif. Chlorination instead transforms the P≡N ligand to a bent [NPCl]– group... (More)

The interstellar diatomic molecule, phosphorus mononitride (P≡N), is highly unstable under conditions typical on Earth, and its utility for constructing elusive P–N π-bonded motifs has remained uncertain. Here, we show how Na(OCP) transfers a P atom to an electrophilic osmium nitride complex to form a metal-bound P≡N ligand. Quantum chemical calculations and X-ray absorption spectroscopy unveil a cumulenic [OsIV=N=P] electronic structure comprising orthogonal Os=N and N=P π-bonding. On reaction with elemental sulfur, the highly reduced P≡N ligand, formally [PN]2–, forms a trigonal planar [NPS2]2– motif. Chlorination instead transforms the P≡N ligand to a bent [NPCl]– group coordinated to OsIII (S = ½). [3 + 2] cycloaddition of this radical with azide forms an aromatic interpnictide, [PN4]–, that is inaccessible from the parent P≡N system. These findings provide a rare glimpse of the divergent reactivity of the alien P≡N molecule, paving the way to long-sought P–N multiple-bonded archetypes.

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author
; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Nature Communications
volume
16
issue
1
article number
5596
publisher
Nature Publishing Group
external identifiers
  • pmid:40595554
  • scopus:105010290733
ISSN
2041-1723
DOI
10.1038/s41467-025-60669-6
language
English
LU publication?
yes
id
1f2e480a-28ca-4ce4-9158-6d8fd1b1a077
date added to LUP
2025-10-27 11:42:56
date last changed
2025-11-10 13:08:53
@article{1f2e480a-28ca-4ce4-9158-6d8fd1b1a077,
  abstract     = {{<p>The interstellar diatomic molecule, phosphorus mononitride (P≡N), is highly unstable under conditions typical on Earth, and its utility for constructing elusive P–N π-bonded motifs has remained uncertain. Here, we show how Na(OCP) transfers a P atom to an electrophilic osmium nitride complex to form a metal-bound P≡N ligand. Quantum chemical calculations and X-ray absorption spectroscopy unveil a cumulenic [Os<sup>IV</sup>=N=P] electronic structure comprising orthogonal Os=N and N=P π-bonding. On reaction with elemental sulfur, the highly reduced P≡N ligand, formally [PN]<sup>2–</sup>, forms a trigonal planar [NPS<sub>2</sub>]<sup>2–</sup> motif. Chlorination instead transforms the P≡N ligand to a bent [NPCl]<sup>–</sup> group coordinated to Os<sup>III</sup> (S = ½). [3 + 2] cycloaddition of this radical with azide forms an aromatic interpnictide, [PN<sub>4</sub>]<sup>–</sup>, that is inaccessible from the parent P≡N system. These findings provide a rare glimpse of the divergent reactivity of the alien P≡N molecule, paving the way to long-sought P–N multiple-bonded archetypes.</p>}},
  author       = {{Edin, Simon and Sandoval-Pauker, Christian and Yutronkie, Nathan J. and Takacs, Zoltan and Wilhelm, Fabrice and Rogalev, Andrei and Pinter, Balazs and Pedersen, Kasper S. and Reinholdt, Anders}},
  issn         = {{2041-1723}},
  language     = {{eng}},
  number       = {{1}},
  publisher    = {{Nature Publishing Group}},
  series       = {{Nature Communications}},
  title        = {{Unleashing phosphorus mononitride}},
  url          = {{http://dx.doi.org/10.1038/s41467-025-60669-6}},
  doi          = {{10.1038/s41467-025-60669-6}},
  volume       = {{16}},
  year         = {{2025}},
}